Patent GB-605724-A (GB)
Title: 4, 4-bis (pyrazolone) couplers for colour photography
IPC: G03C7/384
Filed: 1945-09-13
Abstract: Compounds of the formula <FORM:0605724/IV(b)/1> wherein R represents H or an alkyl, aryl, arylamino, acetarylamido, or aralkyl group, and R1H or an alkyl, aryl, aralkyl, or heterocyclic group are prepared by refluxing together the corresponding mono-pyrazolone with phenylhydrazine.  R may be methyl, ethyl, propyl, butyl, octyl, decyl, heptadecyl, octadecyl, stearyl or other alkyl radical containing up to 24 carbon atoms, carbalkoxyalkyl (e.g. acetic ethyl ester), alkoxycarboxy (e.g. carbomethoxy, carbethoxy and carbopropoxy), phenyl, naphthyl, anthranyl, diphenyl, benzyl, methylbenzyl, ethylbenzyl, amylamino, acetanilido, acetanisido, acetdimethylanilido, acetnaphthylamido, or sulphamylphenylamino, and R1 may be one of the alkyl, aryl, or aralkyl specified for R or thiazolyl, benzthiazolyl, quinolyl, pyridyl, or naphthathiazolyl. The alkyl, aryl, aralkyl, or amino substituted aryl radicals given for R and R1 may be substituted by chlorine, bromine, iodine, acetamido, imino, nitro, alkoxy (e.g. methoxy, ethoxy, propoxy, or butoxy), amino (e.g. primary amino, secondary amino such as methylamino and phenylamino, or tertiary amino such as dimethylamino or diphenylamino), sulphonamino, sulphonic acid, or carboxylic acid groups.  4 : 41-Bis-(phenyl-3-methyl-5-pyrazolone) is prepared by refluxing together 1-phenyl-3-methyl - 5 - pyrazolone and phenylhydrazine.  4 : 41-Bis-(3-methyl-5-pyrazolone), 4 : 41-bis-(1-phenyl-3-phenyl-5-pyrazolone), 4 : 41-bis-(1-p-tolyl-3-methyl-5-pyrazolone), 4 : 41-bis-(1-41-ethoxyphenyl-3-methyl-5-pyrazolone), 4 : 41-bis-(1-41-nitrophenyl-3-methyl-5-pyrazolone), 4 : 41-bis - (1 - (-naphtyl-41-sulpho)-3-methyl-5-pyrazolone), 4 : 41-bis-(1 - 41-sulphophenyl-3-methyl-5-pyrazolone), 4 : 41-bis-(1-phenyl-3-heptadecyl-5-pyrazolone), 4 : 41-bia-(1-41-sulphophenyl-3-heptadecyl-5-pyrazolone), 4 : 41-bis-(1-phenyl-5-pyrazolone-3-acetic ethyl ester), 4 : 41-bis-(1-b -naphthyl-3-p-chloroacetanilido-5-pyrazolone), 4 : 41-bis-(1-phenyl-3-acet- -naphthylamido-5-pyrazolone), 4 : 41-bis-(3-anilino-5-pyrazolone), 4 : 41-bis-(1-phenyl-3-p-anisylamino 5-pyrazolone), 4 : 41-bis-(1-31-carboxyphenyl-3-heptadecyl-5-pyrazolone), 4 : 41-bis-(1- -quinolyl-3-anilino-5-pyrazolone), and 4 : 41-bis-(1-ethanesulphonic acid - 3 - methyl - 5 - pyrazolone) are similarly prepared.  Other bis-pyrazolones referred to are 4 : 41-bis-(1-x-naphthyl-3-methyl-5-pyrazolone), 4 : 41-bis-(1-bromophenyl-3-methyl-5-pyrazolone), 4 : 41-bis-(1-phenyl-3-acetanilido-5-pyrazolone), 4 : 41-bis-5-pyrazolone, 4 : 41-bis-(1-phenyl-3-p-chloracetanilido-5-pyrazolone), 4 : 41-bis-(1-b -naphthyl-3-acetic ethyl ester-5-pyrazolone), 4 : 41-bis-(1-b -naphthyl-3-acet-o-anisido-5-pyrazolone), 4 : 41-bis-(1-p-tolyl-3-(acet-21 : 41-dimethylanilido)-5-pyrazolone), 4 : 41-bis-(1-acetyl-3-anilino-5-pyrazolone), 4 : 41-bis-(3 - o - bromanilino - 5 - pyrazolone), 4 : 41-bis-(3-n-amylamino-5-pyrazolone), 4 : 41-bis-(1-benzoyl-3-anilino-5-pyrazolone), 4 : 41-bis-(1-phenyl-3-anilino-5-pyrazolone), 4 : 41-bis-(1-phenyl-3-p-sulphamylphenylamino-5-pyrazolone), 4 : 41-bis-(1-phenyl-3-p-(p-tert.-amylphenoxy) - phenylamino - 5 - pyrazolone), 4 : 41-bis-(1-31-sulphophenyl-3-heptadecyl-5-pyrazolone), 4 : 41-bis-(1-31-carboxyphenyl-3-undecyl-5-pyrazolone), 4 : 41-bis-(1-ethanesulphonic acid-3-p-nitrophenyl-5-pyrazolone), 4 : 41-bis-(1-ethanesulphonic acid-3-heptadecy-5-pyrazolone), 4 : 41-bis-(1-21-benzthiazolyl-3-anilino-5-pyrazolone), 4 : 41-bis-(1- -pyridyl-3-anilino-5-pyrazolone), 4 : 41-bis-(3-methyl-5-pyrazolone), 4 : 41-bis-(1-(21-methylphenyl-51-sulphonic acid - 3 - heptadecyl - 5 - pyrazolone), 4 : 41-bis-(1-(21-methoxyphenyl-51-sulphonic acid)-3-(31-stearylaminophenyl)-5-pyrazolone), and 4 : 41-bis-(1-(21-phenoxyphenyl-31-sodium sulphonate)-3-heptadecyl-5-pyrazolone).  4 - Nitrophenoxybenzene - 2 - sulphonic acid is prepared by boiling together 1-chloro-4-nitrobenzene-2-sulphonic acid, phenol, sodium carbonate and water.  4 - Aminophenoxybenzene-2-sulphonic acid is prepared by reducing 4-nitrophenoxybenzene-2-sulphonic acid with iron and HCl. 4-Phenoxyphenylhydrazine-3-sulphonic acid is prepared by reducing diazotized 4-aminophenoxybenzene-2-sulphonic acid with sodium bisulphite and potassium hydroxide and heating with HCl.  1 - (41-Phenoxyphenyl-31-sulphonic acid)-3-heptadecyl-5-pyrazolone is prepared by heating 4-phenoxyphenylhydrazine-3-sulphonic acid with ethyl stearyl acetate and glacial acetic acid.  2 - Methylphenylhydrazine - 5 - sulphonic acid (from 2-methylaniline-5-sulphonic acid), 1-(21-methylphenyl-51-sulphonic acid)-3-heptadecyl-5-pyrazolone, 2-methoxyphenylhydrazine-5-sulphonic acid, 1-(21-methoxyphenyl-51-sulphonic acid)-3-(31-nitrophenyl)-5-pyrazolone (using ethyl 3-nitrobenzoylacetate), 1 - (21-methoxyphenyl-51-sulphonic acid)-3-(31-aminophenyl)-5-pyrazolone, and 1 - (21-methoxyphenyl-51-sulphonic acid)-3-(31-stearylaminophenyl)-5-pyrazolone are similarly prepared. 1-(21-Benzthiazolyl)-3-amino-5-pyrazolone is prepared by refluxing together 2-benzthiazolylhydrazine, ethyl cyanacetate, sodium methylate and ethanol.  1-(21-Benzthiazolyl)-3-anilino-5-pyrazolone is prepared by refluxing together 1-(21-benzthiazolyl)-3-amino-5-pyrazolone and aniline. 1-(a -Quinolyl)-3-amino-5-pyrazolone, 1-(x-Quinolyl)-3-anilino-5-pyrazolone, 1-(a -pyridyl)-3-amino-5 pyrazolone, and 1 - (x-pyridyl)-3-anilino-5-pyrazolone are similarly prepared.  1-(-Naphthyl-41-sulphonic acid)-3-methyl-5-pyrazolone is prepared by condensing a -naphthylhydrazine-4-sulphonic acid with ethyl acetoacetate.